Polysubstituted 2-morpholones

ABSTRACT

An essentially single stage reaction has been discovered in which a disubstituted ethanolamine, that is, a 2,2&#39;-substituted-2-aminoethanol, may be reacted with a haloform and a carbonyl containing compound selected from the group consisting of monoketones and benzaldehyde, in the presence of an alkali metal hydroxide, and optionally in the presence of a phase transfer catalyst, to produce an alkali metal hydroxyethylaminoacetate (&#34;HEAA&#34;) which has N-adjacent C atoms on which there are a total of at least three substituents (hence &#34;polysubstituted&#34;), and one or both pairs of substituents on each N-adjacent C atom may be cyclized. The HEAA may be cyclized by the action of a mineral acid to produce a 2-morpholone hydrochloride which is characterized by having a total of at least three substituents on the N-adjacent C atoms of the ring. The 2-morpholone so produced may be reduced to a polysubstituted aminodiol. The aminodiol so produced may be cyclized with an alkane sulfonic acid to yield a polysubstituted morpholine which could not otherwise have been made. The aminodiol may also be alkylated to produce diethers with polysubstituted N-adjacent C atoms. If the aminodiol is tosylated, a polysubstituted crown ether is produced with plural polyalkylene groups. The foregoing HEAA and related compounds are used as u-v light stabilizers in novel compositions in which a small but effective amount of one or more of the HEAA and related compounds is incorporated, in an amount sufficient to produce desirable stabilization against degradation by u-v light in a wide variety of organic materials.

This is a division, of application Ser. No. 101,523, filed Sept. 28,1987 now U.S. Pat. No. 4,914,232 which is a continuation-in-part of Ser.No. 06/750,438 filed 7-1-85 now abandoned which is a division of Ser.No. 06/367,631 filed 4-12-82 now U.S. Pat. No. 4,528,370.

BACKGROUND OF THE INVENTION

Substituted morpholines are commercially available and widely used asdispersing agents for waxes and the like. These morpholines are easilyprepared from substituted diethanolamines by closing the ring.

Substituted morpholin-2-ones ("2-morpholones") on the other hand, arerelatively uncommon compounds known to be useful in pharmaceuticalpreparations, and not easily prepared. Such 2-morpholones areconventionally prepared as described in Heterocyclic Compounds, Vol. 6,by Robert C. Elderfield in the chapter entitled "The MonocyclicOxazines", John Wiley & Sons, Inc. New York (1957).

More recently a mixture of 2-morpholone dimers was produced byirradiation of 5,6-dihydro-3,5,5-trimethyl-1,4-oxazin-2-one in2-propanol solvent at -15° C. (see "An Unusually Weak Carbon-CarbonSingle Bond" by Koch, T. H., Olesen, J. A., and DeNiro, J. in J. Am.Chem. Soc. 97:25, 7285-80, 1979). The mixed dimers were found to bethermally unstable in solution, and in the presence of oxygen the dimerwas rapidly oxidized to 5,6-dihydro-3,5,5-trimethyl-1,4-oxazin-2-one;but prolonged heating in the absence of oxygen gave a mixture of theforegoing oxazine and 3,5,5-trimethylmorpholin-2-one ("morpholone"). Themorpholone so formed must, as a result, have only one substituent on theC atom in the "3" position (C³) of the ring. Though there are two alkylsubstituents on the C⁵ atom of the ring, it will be realized that thesubstituents on this C⁵ atom are necessarily lower alkyl. Thus the priorart monomer is a tri-substituted morpholone with only a singlesubstituent on the C³ atom, and it may not be tetra-substituted withalkyl substituents.

Still more recently, a 5,5-dimethyl-3-phenyl-2-morpholone was preparedwhich was somewhat unstable and existed in equilibrium with aring-opened product identified asmethyl-2-phenyl-2-(1,1-dimethyl-2-hydroxyethyl)aminoacetate (see"Electron-Transfer Chemistry of the Merostabilized3,5,5-Trimethyl-2-morpholinon-3-yl Radical" by Burns, J. M., Wharry, D.L. and Koch, T. H., J. Am. Chem. Soc., 103, 849-856, 1981), but notethat the 3-position cannot be disubstituted.

Research probing the reactions of the dimers resulted in the knowledgethat a mixture of meso and dl dimers heated with2,2'-azobis(2-methylpropionitrile) produced[2'-(2'-cyanopropyl)]-3,5,5-trimethylmorpholin-2-one. This cyanoalkylsubstituted-trimethylmorpholone and thephenyl-substituted-trimethylmorpholone are the only tetra-substituted2-morpholones known. The substituents on the N-adjacent C atoms cannotbe changed because of the recognized relative instability of the lactonering. For example, it has been found that this ring can neither bereduced nor oxidized without opening it. Thus, I know neither of anytri- or tetra-substituted morpholines which may be derived from known2-morpholones, nor of any 2-morpholones which can be derived byreplacement of the cyanoalkyl or phenyl substituents on the C³ atom byanother substituent without disrupting the lactone ring. Nor do I knowof any method for preparing a C³ -cyanoalkyl-substituted-2-morpholone orC³ -phenyl-substituted-2-morpholone, with other than lower alkylsubstituents on the C⁵ atom of the lactone ring.

Stated differently, it was not heretofore known how polysubstitutedcompounds may be prepared which have either (a) three substituents whichare not lower alkyl, or, (b) three substituents, one of which on C³ isphenyl or cyanoalkyl, and at least one of the remaining two substituentson the other N-adjacent C atom is not alkyl, or, (c) four substituentsall of which may be alkyl, on the (combined) N-adjacent C atoms. Theterm "polysubstituted" is specifically used in this specification toconnote that in the claimed compounds of this invention, a total ofthree or more substituents is necessarily present on the two N-adjacentC atoms, combined; and, two substituents, which may be cyclized, arealways present on the C³ atom when the compound is a 2-morpholone. Inthis sense, it will be recognized that if each of the substituents onthe one N-adjacent C atom are cyclic substituents, and the substituentson the other N-adjacent C atom are not, then there are a total of foursubstituents; there are also four substituents if the two substituentson each N-adjacent C atom are together cyclized.

The problem with preparing polysubstituted 2-morpholones carries over tothe preparation of polysubstituted morpholines. For example, it is knownthat reductive alkylation of HOCH₂ C(CH₃)₂ NH₂ with CH₃ COCH₂ OH yields[(HOCH₂ C(CH₃)₂ ]NH[CH(CH₃)CH₂ OH] which upon cyclization by heatingwith conc H₂ SO₄ produces 3,5,5-trimethylmorpholine (see 112872h Chem.Abstr. Vol 71, pg 374, 1979), but this approach cannot produce atrimethyl-2-morpholone.

The key to providing three or more substituents on the combinedN-adjacent C atoms, is to provide the polysubstituents on the C atomsbefore the ring is closed. Only a few such polysubstituted compounds areknown. In these known compounds, only specific substituents may bepresent because of the manner in which the compounds are necessarilyprepared. Such compounds are3-[2'-(2'-cyanopropyl)]-3,5,5-trimethylmorpholin-2-one, prepared asdescribed in the Koch et al. articles, supra; and,5,5-dimethyl-3-phenyl-2-morpholinone, prepared as described in the Burnset al article, supra. Though sodium hydroxyethylaminoacetate is easilyprepared, and two substituents may be made on one or the otherN-adjacent C atom, or, one substituent may be made on one and also (one)on the other N-adjacent C atom, polysubstitutedhydroxyethylaminoacetates ("HEAA" for brevity) having three or moresubstituents have not been known or made because of the steric hindranceproblems, inter alia. Further, though polysubstituted aminodiols such as[HOCH₂ C(CH₃)₂ ]NH[CH(CH₃)CH₂ OH] are known, I know of no apparentlyoperable method for converting such aminodiols to N-hydroxyalkylaminoacids. As a result, tri-substituted or tetra-substituted N-adjacent Catoms of an alkali metal hydroxyethylaminoacetate are not known.

Hindered amines, to which general class the compounds of this inventionbelong, are known to have utility as u-v light stabilizers in syntheticresins subject to actinic radiation. However, not all hindered aminesare effective stabilizers against u-v light degradation in normallysolid polymers. Some hindered amines are thermally unstable at as low as100° C. which precludes their use in any organic material which isprocessed at or above that temperature. Further, particularly withpolysubstituted heterocyclic ring compounds, N atoms in the ring areknown to have a beneficial effect but there is no more reason to expectthat a polysubstituted morpholone might be effective than there is tobelieve that a polysubstituted thiomorpholine might be effective. Moreparticularly, it was known that dimers of5,6-dihydro-3,5,5-trimethyl-1,4-oxazin-2-one are photoreductive andthermally unstable in solution when heated to 80° C., and that insolution, these dimers exist in equilibrium with a radical at roomtemperature (Koch et al, supra). Therefore, it was quite surprising thata polysubstituted 2-morpholone or a polysubstituted related compound,would provide excellent u-v light stability.

Because of the unpredictability of the effectiveness of various hinderedamines solely based on their (hindered) structure, much effort has beenexpended to synthesize hindered amines which must then be tested forpossible utility as u-v light stabilizers. One of the synthesis isdescribed in an article titled "Hindered Amines. Novel Synthesis of1,3,3,5,5-Pentasubstituted 2-Piperazinones" by John T. Lai in J. Org.Chem. 45, 754 (1980). The concept of retaining the "2-keto" ringstructure of a heterocyclic ring containing at least one N atom was thebasis upon which the search for effective 2-morpholones was initiated.The necessity of providing more than two substituents on the N-adjacentC atoms spurred the discovery of the application of a "ketoformsynthesis" to solve the problem. This invention derives from furtherresearch in the field of the synthesis of hindered amines, and anevaluation of their effectiveness as u-v light stabilizers.

Hindered amines of the prior art are generally complex compounds notprepared with notable ease, and their properties, particularly theircompatability in various synthetic resins, is difficult to predict.Apparently small differences in structure, result in large differencesin performance. Prolonged efforts to provide simpler compounds which arerelatively easily prepared, have resulted in the2-keto-1,4-diazacycloalkanes and the 2-keto-1,5-diazacycloalkanesdisclosed in U.S. Pat. Nos. 4,190,571 and 4,207,228.

The present invention is particularly directed to (a) novelpolysubstituted alkali metal hydroxyethylaminoacetates, (b) a novelsynthesis for a polysubstituted alkali metal hydroxyethylaminoacetate,(c) novel compositions in which a polysubstituted alkali metalhydroxyethylaminoacetate is incorporated, (d) novel polysubstituted2-morpholones, (e) a novel synthesis for polysubstituted 2-morpholones,(f) novel compositions stabilized against u-v light degradation by thepresence of a stabilizing amount of the 2-morpholones, (g) novelpolysubstituted aminodiols, (h) novel compositions stabilized againstu-v light degradation by the presence of a small but effective amount ofa polysubstituted aminodiol, (i) novel polysubstituted monoaza crownethers, (j) synthesis of polysubstituted monoaza crown ethers, (k) novelcompositions stabilized against u-v light degradation by the presence ofan effective amount a polysubstituted monoaza crown ether, (l)polysubstituted morpholine, (m) synthesis of polysubstituted morpholineby cyclization of an aminodiol with an alkanesulfonic acid, (n) novelcompositions stabilized against u-v light degradation by the presencetherein of an effective amount of a polysubstituted morpholine, (o)novel polysubstituted aminodiethers, and (p) novel compositionsstabilized by the presence therein of an effective amount of apolysubstituted aminodiether.

The synthesis of the novel stabilizers of this invention is facilitatedby the peculiar action of certain onium salts in an aqueous alkalinemedium, which action facilitates the interaction of an aminenucleophilic agent such as a primary or secondary amine, with chloroformor other trichloromethide generating agent, and a ketone or aldehyde.The organic onium salts of nitrogen, and phosphorus are well known. Theyare ionized in aqueous solutions to form stable cations. Certain oniumsalts have provided the basis for phase transfer catalysis in a widevariety of reactions, a recent and comprehensive review of which iscontained in Angewandte Chemie, International Edition in English, 16493-558 (August 1977). Discussed therein are various anion transferreactions where the onium salt exchanges its original anion for otheranions in the aqueous phase. These ion pairs can then enter a waterimmiscible, organic liquid phase, making it possible to carry outchemistry there with the transported anion, including OH⁻ ions. Manyreactions involving water immiscible solutions of various simple organicmolecules have been described. Though the use of phase transfercatalysts facilitate the cyclization of an appropriately stericallyhindered branched chain amine having proximate primary and secondaryamine groups amongst plural amine groups in the chain, the reaction hasalso been found to proceed, though relatively slowly, by simply using alarge excess of the ketone or aromatic aldehyde either of which is theessential carbonyl containing compound which contributes the carbonylgroup to the 2-position of the diazacycloalkane ring.

A phase transfer catalyzed reaction known as the "ketoform reaction" isdisclosed in U.S. Pat. No. 4,167,512, which proceeds by virtue of aphase transfer catalyzed reaction mechanism in which an amine, ahaloform and a carbonyl containing ("carbonyl") compound are separatereactants. This reaction is illustrated in one particular example by thereaction of a N,N'-alkyl substituted ethylene diamine with acetone andchloroform; and, in another example, with o-phenylene diamine reactedwith cyclohexanone and chloroform. The reaction product in each exampleis a 2-keto-1,4-diazacycloalkane.

Though both ketones and aldehydes are taught as being effectivereactants in the ketoform reaction, it has now been discovered that onlyketones and benzaldehyde are effective in the formation of HEAA.Accordingly, my present invention is a particular adaptation of theketoform reaction to the preparation of alkali metal HEAA, and severalsuccessor compounds derived therefrom, including 2-morpholones,aminodiols, monoaza crown ethers, and morpholines, all of which arepolysubstituted, and are collectively referred to herein as "HEAAcompounds" for brevity.

Very recently, amino acid mixtures, and their alkali metal salts havebeen prepared as disclosed in U.S. Pat. No. 4,525,294 to Sartori et al.,by reductive condensation or amination. But this reaction requires thatthere must always be a H atom present on each of the carbon atoms oneither side of the N atom in the Sartori structure. As a consequence, asSartori et al teach, the reductive amination of the ketone results inthe H atom on the alpha C atom. There is no known way of substitutingthis H atom.

Also very recently, U.S. Pat. No. 4,542,234 to Reilly et al disclosesthat the C atoms on either side of a N atom may each be substituted ifone starts with an alpha-halo ester and tosylates it. To make my claimedcompound in an analogous manner one would have to tosylate at-butylamine derivative. More specifically, for example, one would haveto react 2-maino-2-methyl-2-propanol with alpha-haloisobutyrate, thentosylate the reaction product. Except that there will be no reactionproduct to tosylate. The reaction product is not formed because ofexcessive hindrance. It should be noted, in this regard, thatdi-isopropylamine is a readily available compound, but di-t-butylamine,which is also known, cannot be made by a reaction analogous to that ofReilly et al. (see "Synthesis of di-t-alkylamines" by E. J. Corey and A.Gross, Tetrahedron Letters Vol 25, pgs 491-494, 1984).

Further in this regard, it is well known that a tertiary alkyl halideundergoes an elimination reaction with any amine. For example, t-butylchloride reacts with t-butylamine to yield isobutylene. When an attemptis made to react alpha-haloisobutyrate with 2-amino-2-methyl-1-propanol,one gets the elimination reaction which yields the methacrylate, not theproduct of a condensation reaction. This is consistent with the textbookteaching that tertiary substrates do not give the alkylation reaction atall, but undergo preferential elimination. (see Advanced OrganicChemistry by Jerry March, bottom of pg 365, 3rd Ed., John Wiley & Sons,1985).

One cannot arrive at the least hindered of secondary amines from atertiary alkyl halide and an amine. Even when one reacts a tertiaryalkyl halide with NCl₃ and AlCl₃, one gets a primary amine, not asecondary amine. (see, March, supra).

SUMMARY OF THE INVENTION

An essentially single stage reaction has been discovered in which adisubstituted ethanolamine, that is, a2,2'-disubstituted-2-aminoethanol, may be reacted with a haloform and acarbonyl containing compound selected from the group consisting ofmonoketones and an aromatic monoaldehyde (araldehyde) having from 7 toabout 9 carbon atoms, in the presence of an alkali metal hydroxide, andoptionally in the presence of a phase transfer catalyst, to produce analkali metal hydroxyethylaminoacetate ("HEAA") which has N-adjacent Catoms on which there are a total of at least three substituents (hence"polysubstituted"), and one or both pairs of substituents on eachN-adjacent C atom may be cyclized.

It has further been discovered that a polysubstituted alkali metal HEAAmay be cyclized by the action of a strong acid, for example concentratedHCl, to produce a 2-morpholone hydrochloride which is characterized byhaving a total of at least three substituents on the N-adjacent C atomsof the ring. By reaction with triethylamine, or other base, apolysubstituted 2-morpholone is produced. Novel polysubstituted2-morpholones are produced in which the C³ position is disubstitutedfrom a wide choice of substituents. If the C³ position ismonosubstituted with phenyl then the C⁵ position is substituted with atleast one substituent which is not lower alkyl; if the C³ position isdisubstituted and one of the two substituents is cyanoalkyl, then the C⁵position is substituted with at least one substituent which is not loweralkyl.

It has still further been discovered that the polysubstituted2-morpholones so produced may be reduced by reaction with LiAlH₄,diborane, or H₂ under pressure in the presence of Raney's nickelcatalyst, to a polysubstituted aminodiol.

It has also been discovered that the aminodiol so produced may becyclized with an alkane sulfonic acid to yield a polysubstitutedmorpholine which could not otherwise have been made, and can now be madeonly by this cyclization reaction.

It has also further been discovered that the aminodiol so produced maybe conventionally alkylated to produce diethers with polysubstitutedN-adjacent C atoms. If the aminodiol is reacted with apolyalkyleneglycol ditosylate, a polysubstituted crown ether is producedwith plural polyalkylene groups.

It is therefore a general object of this invention to provide novelpolysubstituted alkali metal hydroxyethylaminoacetates ("HEAA"), andnovel compounds related thereto, or derived therefrom, all of which arecollectively referred to herein as "HEAA compounds"; to provideprocesses for producing the novel compounds; and, to provide novelcompositions in which a small but effective amount of one or more of theHEAA compounds is incorporated, optionally in addition with antioxidantsynergists, pigments, and other known compounding ingredients, inamounts sufficient to produce desirable stabilization againstdegradation in a wide variety of organic materials.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The polysubstituted structure of the various stabilizer compoundsprepared by the syntheses described herein, is derived by virtue of anadaptation of the ketoform synthesis. This adaptation permits thepreparation of a polysubstituted HEAA without the formation ofisocyanides. As is well known, primary amines react with chloroform inthe presence of NaOH in the carbylamine reaction which is a delicatetest for the presence of a primary amine because of the powerful odor ofthe isocyanides formed. No powerful odor of isocyanide is detected inthe adaptation of the ketoform reaction as used in this invention.

The HEAA is preferably tetra-substituted, though tri-substituted HEAAalso have good u-v stabilization effects in transparent, translucent orlightly colored synthetic resins. Despite the seemingly simple structureof alkali metal HEAA which have at least three substituents on theN-adjacent carbon atoms, these HEAA to my knowledge, can be prepared byno other method than that described hereinbelow.

The structure of an alkali metal HEAA is as follows: ##STR1## wherein,R¹, R², R³ and R⁴ are independently selected from the group consistingof aryl, alkyl each having from 1 to about 24 carbon atoms, cycloalkylhaving from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, etherhaving from 4 to 18 carbon atoms, and hydroxyalkyl having from 1 toabout 18 carbon atoms; so that each C atom on either side of the N atomis disubstituted;

R¹ and R² together, or R³ and R⁴ together, or each pair, may be cyclizedforming a ring having from about 5 to about 8 carbon atoms;

except that not more than one of R¹, R², R³ or R⁴ may be cyclic;

R⁵ is selected from hydrogen, oxygen, hydroxyl and alkyl having from 1to about 24 carbon atoms; and,

M represents an alkali metal.

Process for Preparing an Alkali Metal HEAA

The starting material is a 2,2'-substituted-2-amino-ethanol representedby the following structure: ##STR2## wherein R¹ and R² have the sameconnotation as hereinabove, and R¹ and R² may together be cyclizedforming a ring having from about 5 to about 8 carbon atoms.

As will presently be evident, a wide range of substituents may be madewithout undue difficulty, and the choice of substituents in large part,determines the properties of the compound as a u-v stabilizer. Thisaminoethanol may be only mono-substituted, depending upon the choice ofa ketone as a reactant in the reaction to be described hereinbelow, butbest results are obtained when the aminoethanol is di-substituted, whichincludes the case where R¹ and R² are cyclized. Since the aminoethanolis a primary amine it will be apparent that any substituent desired onthe N atom will have to be made after the formation of thepolysubstituted alkali metal hydroxyethylaminoacetate ("HEAA") as setforth hereunder.

This aminoethanol is reacted with (i) at least one molar equivalent of ahaloform selected from the group consisting of chloroform and bromoform,and (ii) at least one molar equivalent of a carbonyl containing compoundselected from the group consisting of monoketones and an aromaticmonoaldehyde ("araldehyde") which may be ring substituted having from 7to about 9 carbon atoms, optionally (iii) in the presence of a phasetransfer catalyst, and, necessarily with (iv) at least one molarequivalent of an alkali metal hydroxide so as to form the alkali metalHEAA. The preferred temperature of the reaction with a ketone is in therange from about -10° C. to about 30° C. at ambient pressure, and fromabout 10° C. to about 60° C. with an araldehyde. Some reactions may bepreferably carried out under elevated pressure, and others under vacuum,but in general, pressure plays only its expected role in the progress ofthe reaction.

The HEAA compounds of this invention are hindered amines and undergo theexpected reactions which hindered amines are known to undergo. Forexample, the hydrogen on the N atom may be replaced with an alkyl grouphaving from 1 to about 24 carbon atoms, by conventional alkylation; or,the H may be replaced by oxygen by reaction of the HEAA withmetachloroperbenzoic acid; in turn, it will be appreciated, that thealkyl group or oxygen so introduced on the N atom, may be furtherreacted, conventionally, to give additional substituents.

Process for Preparing Polysubstituted 2-Morpholones

The alkali metal HEAA prepared as described hereinabove may be cyclizedwith a cyclization agent to yield a 2-morpholone which retains thesubstituents on the N-adjacent atoms. The polysubstituted 2-morpholonehas the following structure: ##STR3## wherein, R¹, R², R³ and R⁴ areindependently selected from the group consisting of aryl, alkyl havingfrom 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkylhaving from 2 to about 12 carbon atoms, ether having from 4 to about 18carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms;

R¹ and R² together, or R³ and R⁴ together, or each pair, may be cyclizedforming a ring having from about 5 to about 8 carbon atoms; and,

R⁵ is selected from hydrogen, oxygen and alkyl having from 1 to about 24carbon atoms, and hydroxyl;

except that not more than one of R¹, R², R³ or R⁴ may be hydrogen; andno more than three of R¹, R², R³ and R⁴ may be cyclic; further, if oneof R³ and R⁴ is H or lower alkyl having from 1 to about 6 carbon atomsand the other is phenyl or cyanoalkyl, then at least one of R¹ and R² isnot alkyl.

Cyclization is preferably effected by contacting the alkali metal HEAAwith strong acid, for example concentrated HCl. The 2-morpholonehydrochloride so formed may then be reacted with triethylamine to removethe HCl and form the 2-morpholone. The temperature at which the reactionis carried out may be in the range from from about -10° C. to about 100°C.

Process for Preparing Polysubstituted Aminodiols

The polysubstituted 2-morpholones prepared as described hereinabove maybe reduced with a suitable reducing agent to yield a polysubstitutedaminodiol having the structure: ##STR4## wherein, R¹, R², R³ and R⁴ areindependently selected from the group consisting of aryl, alkyl eachhaving from 1 to about 24 carbon atoms, cycloalkyl having from 5 toabout 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms,cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4to 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbonatoms, so that each C atom on either side of the N atom isdisubstituted;

R¹ and R² together, or R³ and R⁴ together, or each pair, may be cyclizedforming a ring having from 5 to about 8 carbon atoms;

R⁵ is selected from hydrogen, oxygen, and alkyl having from 1 to about24 carbon atoms, and hydroxyl;

except that not more than three of R¹, R², R³ or R⁴ may be cyclic.

The reduction of the polysubstituted 2-morpholone may be effected by anyconventional reaction such as reduction with diborane, or LiAlH₄, ormore preferably, with H₂ under pressure in the presence of a Raney'snickel catalyst, any of which reactions result in opening of the lactonering rather than formation of the morpholine. If reduced with LiAlH₄ thereactants are dissolved in THF and refluxed for several hours. Aftercooling, the reaction mixture is neutralized with dilute NaOH solutionto yield the aminodiol which is normally solid.

Process for Preparing Polysubstituted Monoaza Crown Ethers

The polysubstituted aminodiol prepared as described hereinabove may becyclized so as to include a polyalkylene oxide bridge, by reaction witha polyalkylenediol with terminal leaving groups, so as to yield amonoaza crown ether. This reaction is quite unexpected because it occursdespite the hindrance of the substituents on the N-adjacent atom of theaminodiol. The monoaza crown ether formed upon cyclization isrepresented by the structure: ##STR5## wherein, R¹, R², R³ and R⁴ areindependently selected from the group consisting of aryl, alkyl havingfrom 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkylhaving from 2 to about 12 carbon atoms, ether having from 4 to about 18carbon atoms, and hydroxyalkyl having from 2 to about 18 carbon atoms;

R¹ and R² together, or R³ and R⁴ together, or each pair, may be cyclizedforming a ring having from about 5 to about 8 carbon atoms; and,

R⁵ is selected from hydrogen, oxygen and alkyl having from 1 to about 24carbon atoms, and hydroxyl;

except that not more than one of R¹, R², R³ or R⁴ may be hydrogen; andno more than three of R¹, R², R³ and R⁴ may be cyclic; and, x and n areintegers in the range from 2 to 4.

The polyalkylene oxide bridge is preferably introduced into the monoazacrown ether ring by tosylation with a ditosylglycol. Though there may bethree methylene groups, most preferred are two, that is, a polyethyleneoxide bridge.

Process for Preparing Polysubstituted Morpholines

The aminodiol obtained as described hereinabove may be cyclized byreaction with an alkane sulfonic acid to yield a polysubstitutedmorpholine having the structure: ##STR6## wherein, R¹, R², R³ and R⁴ areindependently selected from the group consisting of aryl, alkyl eachhaving from 1 to about 24 carbon atoms, cycloalkyl having from 5 toabout 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms,cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4to 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbonatoms, so that each C atom on either side of the N atom isdisubstituted;

R¹ and R² together, or R³ and R⁴ together, or each pair, may be cyclizedforming a ring having from 5 to about 8 carbon atoms;

R⁵ is selected from hydrogen, oxygen, and alkyl having from 1 to about24 carbon atoms, and hydroxyl;

except that not more than three of R¹, R², R³ or R⁴ may be cyclic.

Only an alkane sulfonic acid is effective to cyclize the aminodiol, andlower alkane sulfonic acids having from 1 to about 5 carbon atoms arepreferred. Most preferred is methane sulfonic acid which is heated to atemperature in the range from about 100° C. to about 150° C. to cyclizethe aminodiol. The reaction occurs over a period of about 10 hr, afterwhich the reaction mixture is cooled down and 10% NaOH is added. Uponworking up the mixture to recover the pure polysubstituted morpholine, acolorless oil is usually obtained.

Process for Preparing Polysubstituted Aminodiethers

The aminodiol obtained as described hereinabove may be converted to anaminodiether by reaction with an alkyl iodide or dimethyl sulfate, afterfirst heating the aminodiol to reflux in an aromatic solvent such astoluene, in the presence of a stong base, such as sodium hydride, underan inert atmosphere. The aminodiether obtained may be worked up byadding water, extracting the aqueous solution with toluene, drying thecombined toluene solutions with sodium sulfate, and concentrating. Theaminodiether is isolated by simple distillation.

The structure of a polysubstituted aminodiether is as follows: ##STR7##wherein, R¹, R², R³ and R⁴ are independently selected from the groupconsisting of aryl, alkyl each having from 1 to about 24 carbon atoms,cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbonatoms, ether having from 4 to 18 carbon atoms, and hydroxyalkyl havingfrom 1 to about 18 carbon atoms, so that each C atom on either side ofthe N atom is disubstituted;

R¹ and R² together, or R³ and R⁴ together, or each pair, may be cyclizedforming a ring having from 5 to about 8 carbon atoms;

R⁵ is selected from hydrogen, oxygen, and alkyl having from 1 to about24 carbon atoms, and hydroxyl;

except that not more than three of R¹, R², R³ and R⁴ may be cyclic, and,

R⁶ and R⁷ are independently selected from the group consisting of alkylhaving from 1 to about 24 carbon atoms, and aralkyl having from 7 toabout 24 carbon atoms.

The polysubstituted HEAA compounds are generally crystalline solidssoluble in acetone, diethyl ether, dioxane, tetrahydrofuran, carbontetrachloride, chloroform, lower primary alcohols having from 1 to about6 carbon atoms such as methanol, ethanol and propanol, aromatichydrocarbons such as benzene and toluene, but much less soluble inaliphatic hydrocarbons such as hexane. Some HEAA-derived compounds areoily lightly colored liquids. Many are quite soluble in water and areespecially useful when they are to be disperesed in a latex to bestabilized against u-v light degradation. The alkali metal salts rangein color from water-white to brown when pure, but when dispersed in anorganic material, particularly in polyolefins, polyamides, and polyvinylaromatics, at a concentration of less than 5 parts per 100 parts byweight of organic material, the color of the HEAA in the composition isnot noticeable.

The amount of the stabilizer employed will vary with the particularmaterial to be stabilized and also the polysubstituted HEAA orHEAA-related stabilizer employed. Generally however, for effective u-vlight stabilization of most organic materials, an amount of thestabilizer used is in the range from about 0.001 percent to about 10percent by weight (% by wt) based on the weight of organic material. Intypical stabilized compositions the amount of polysubstituted stabilizerused is in the range from about 0.01 to about 5% by wt.

Compositions of this invention are synthetic resinous materials whichhave been stabilized to combat the deleterious effects of uv light,thermal or oxidative degradation such as are usually evidenced bydiscoloration and/or embrittlement. These compositions generally benefitfrom the inclusion of additional, secondary stabilizers to achieve evengreater stability against a combination of actinic light, heat andoxygen. Therefore, in conjunction with the stabilizers of thisinvention, compositions may include stabilizers against degradation byheat and/or oxygen which secondary stabilizers may be present in therange from about 0.1 part to about 10 parts by weight, and preferablyfrom about 0.2 part to about 5 parts by weight per 100 parts by weightof the organic continuous phase. Several types of known UV secondarystabilizers may be used, such as those disclosed in U.S. Pat. Nos.3,325,448; 3,769,259; 3,920,659; 3,962,255; 3,966,711; 3,971,757; interalia.

Organic materials which may be stabilized against uv light, thermal andoxidative degradation, include copolymers of butadiene with acrylicacid, alkyl acrylates or methacrylates, polyisoprene, polychloroprene,and the like; polyurethanes; vinyl polymers known as PVC resins such aspolyvinyl chloride, copolymers of vinyl chloride with vinylidenechloride, copolymers of vinyl halide with butadiene, styrene, vinylesters, and the like; polyamides such as those derived from the reactionof hexamethylene diamine with adipic or sebacic acid; epoxy resins suchas those obtained from the condensation of epichlorohydrin withbisphenols, and the like; ABS resins, polystyrene, polyacrylonitrile,polymethacrylates, poly-carbonates, varnish, phenol-formaldehyde resins,polyepoxides, polyesters, and polyolefin homo- and copolymers such aspolyethylene, polypropylene, ethylene-propylene polymers,ethylene-propylenediene polymers, ethylene-vinyl acetate polymers, andthe like. The polysubstituted HEAA compounds can also be used tostabilize mixtures and blends of polymeric materials such as ABS resinblends, PVC and polymethacrylate blends, and blends of polyolefinhomopolymers and copolymers such as blends of polypropylene in epdmpolymers.

Most particularly substituted HEAA and HEAA-derived compounds of thisinvention having at least three and preferably four substituents on theN-adjacent C atoms, including of course if the substituents arecyclized, are especially useful as uv-light-stabilizers for syntheticresinous materials which are at least partially permeable to visiblelight, and particularly for those which are transparent thereto, such asthe polyvinylaromatics and polyolefins. It will be recognized that ifeach of the substituents R¹ and R² on the N-adjacent C atom arecyclized, and the R² and R³ substituents of the other N-adjacent C atomare not, then, in the sense used herein, there are still foursubstituents, as is also the case if the substituents R³ and R⁴ arecyclized.

Many known compounding ingredients may be used along with thesubstituted PIP-T stabilizers in the compositions. Such ingredientsinclude metal oxides such as zinc, calcium and magnesium oxide, fattyacids such as stearic and lauric acid, and salts thereof such ascadmium, zinc and sodium stearate and lead oleate; fillers such ascalcium and magnesium carbonate, calcium and barium sulfates, aluminumsilicates, asbestos, and the like; plasticizers and extenders such asdialkyl and diaryl organic acids like diisobutyl, diisooctyl,diisodecyl, and dibenzyl oleates, stearates, sebacates, azelates,phthalates, and the like; ASTM type 2 petroleum oils, paraffinic oils,castor oil, tall oil, glycerin, and the like.

Particularly desirable secondary stabilizers are one or moreantioxidants used in the range from about 0.1 part to about 20 parts byweight, preferably from about 0.2 part to about 5 parts by weight per100 parts by weight of the material. Of the types of antioxidants to beused, are phosphite, phosphate, sulfide and phenolic antioxidants, thelast being preferred. Most preferred are phenolic antioxidants such as2,6-di-t-butyl paracresol; 2,2'-methylene-bis-(6-t-butyl-phenol);2,2'-thiobis-(4-methyl-6-t-butyl-phenol);2,2'-methylene-bis-(6-t-butyl-4-ethyl-phenol);4,4'-butylene-bis-(6-t-butyl-m-cresol);2-(4-hydroxy-3,5-di-t-butylanilino)-4,6-bis-(octylthio)-1,3,5-triazine;hexahydro-1,3,5-tris-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyl-s-triazine;hexahydro-1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate;tetrakismethylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionatemethane; and other antioxidant synergists such as distearylthiodipropionate; dilauryl thiodipropionate; tri(nonylphenyl) phosphite;tin thioglycolate; and particularly commercially available antioxidantssuch as Goodrite® 3114, and 3125, Irganox 1010, 1035, 1076 and 1093.Other ingredients such as pigments, tackifiers, flame retardants,fungicides, and the like may also be added.

The polysubstituted HEAA stabilizers, and the other compoundingingredients if used, can be admixed with organic materials using knownmixing techniques and equipment such as internal mixing kettles, aBanbury mixer, a Henschel mixer, a two-roll mill, an extruder mixer, orother standard equipment, to yield a composition which may be extruded,pressed, blowmolded or the like into film, fiber or shaped articles.Usual mixing times and temperatures can be employed which may bedetermined with a little trial and error for any particular composition.The objective is to obtain intimate and uniform mixing of thecomponents. A favorable mixing procedure to use when adding apolysubstituted HEAA to an organic material is either to dissolve orsuspend the compound in a liquid such as hexane or benzene before addingit, or to add the HEAA directly to the polymeric organic materialwhether the HEAA is in the form of a powder or oil, or to extruder-mixthe HEAA and the polymeric material prior to forming the product.

The u-v stability of a particular composition containing a polymericmaterial and a polysubstituted HEAA can be evalutated by exposing aprepared sample of the composition to Xenon or carbon arc light in aWeather-O-meter operating at a temperature, for example, about 140° F.(60° C.). Degradation of the sample can be followed by periodicallymeasuring tensile strength left, and the hydroperoxide absorption bandat 3460 cm⁻¹ or carbonyl absorption band at 1720 cm⁻¹ using an IRspectrophotometer. The rapid formation of carbonyl indicates failure ofthe sample. The test procedure is well known, and is published in thetext Photodegradation, Photo-oxidation and Photostabilization ofPolymers by Ranby and Rabek, John Wiley & Sons, N.Y., N.Y. (1975), atpages 129 et seq., and is disclosed in U.S. Pat. No. 3,909,493. Failureof the sample is also checked by visual signs of cracking when thesample is bent 180°.

Samples of the compositions can also be checked for oxidative andthermal stability by measuring the time to discoloration and/orembrittlement of the sample after aging in an air circulating oven at140° C., and other standard ASTM tests.

The following Table I sets forth data obtained in tests conducted with 2mil thickness samples of polypropylene. The blank and each sampleincludes 0.05 parts per hundred parts of resin (`phr`) of Goodrite* 3125antioxidant, and the amount of stabilizer used in each sample is stated.Oven aging is done continuously at 125° C. in the standard testprocedure, and the Weather-O-Meter tests give the number of hours afterwhich a sample loses 50% of its tensile strength. Test compositions ofthis invention were removed from the oven after having withstood 33days, and were removed from the Weather-O-Meter after having withstoodmore than 2000 hr without losing 50% of their tensile strength. Theresults documented simply indicate that the samples withstood more than33 days of oven aging, and more than 2000 Weather-O-Meter exposure.Chimasorb® 944 is a commercially available polytriazine havingpiperidine substituents disclosed in U.S. Pat. No. 4,086,204. Cyasorb®531 is also a commercially available stabilizer (from American CyanamidCo.) having a benzo phenonestructure.

                                      TABLE I                                     __________________________________________________________________________                          Amount                                                                             Oven aging                                                                          Failure*                                     Ex.                                                                              Stabilizer used    (phr)                                                                              (days)                                                                              (hr)                                         __________________________________________________________________________    1  Blank              0    25      870                                        2  Cyasorb 531        0.1  25     1760                                        3  Chimasorb 944      0.1  25     1860                                        4  sodium tetramethyl-hydroxyethylamino                                                             0.1  33    >2000                                           acetate ("4M-HEAA")                                                        5  3,3,5,5-tetramethyl-2-morpholone                                                                 0.1  33    >2000                                        6  3,3-pentamethylene-5,5-dimethyl-2                                                                0.1  33    >2000                                           morpoholone                                                                7  3-ethyl-3,5,5-trimethyl-2-morpholone                                                             0.1  33    >2000                                        8  di-(1-hydroxy-2-methyl-2-propyl)amine                                                            0.1  33    >2000                                        9  3,3,5,5-tetramethyl-morpholine                                                                   0.1  33    >2000                                        __________________________________________________________________________     *tensile strength was about 50% of original                              

EXAMPLE 1 A. Preparation of sodium tetramethyl-hydroxyethylaminoacetate("4M-HEAA") having the structure ##STR8##

2-amino-2-methyl-1-propanol (0.6 mole), chloroform (0.8 mole), acetone(2.4 mole) and benzyltriethylammonium chloride (0.018 mole) are placedin a three-necked flask cooled in a circulating ice bath so that thetemperature is maintained in the range from about 0°-5° C. Aqueoussodium hydroxide (50% solution) is added dropwise into the contents ofthe flask while they are stirred. It is preferred to add at least fourmoles of NaOH for each mole of 2-amino-2-methyl-1-propanol, and asubstantial excess over four equivalents is best. Also, in excess of oneequivalent of chloroform is used, and nearly two equivalents is better.The phase transfer catalyst may be dispensed with in some instances if avery large excess of ketone is used as a reactant.

Stirring is continued overnight and the reaction mixture is filtered.The solid recovered is a mixture of 4M-HEAA and NaCl, but some of eachmay still be present in the filtrate. The organic phase is separatedfrom the aqueous phase of the filtrate, and the ketone is recovered fromthe organic phase. If there is any 4M-HEAA in either the organic oraqueous phases, it may be recovered therefrom in any conventionalmanner. The solid is rinsed with methylene chloride to dissolveremaining organic phase on the solids which are then stirred into 300 mlmethanol in which the 4M-HEAA dissolves but the NaCl does not. Crude4M-HEAA is recovered from the methanol as a solid. Upon analysis, it isconfirmed that the solid obtained is sodiumtetramethyl-hydroxyethylaminoacetate.

The compound 4M-HEAA is found to have excellent stabilization propertiesagainst u-v light degradation as is evident from the test results whenit is incorporated in polypropylene, which results are set forth inTable I hereinbefore.

B. Preparation of sodium2-[2-methyl-1-hydroxy-2-propylamino]-2-butanoate

In a manner analogous to that described in example 1A hereinabove,2-butanone is substituted for acetone, and the reaction similarlycarried out. Analysis of the product confirms its identificationhereinabove.

C. Preparation of sodium2-[2-methyl-1-hydroxy-2-propylamino]-2-cyclohexyl carboxylate having thefollowing structure ##STR9##

In a manner analogous to that described in example 1A hereinabove,cyclohexanone is substituted for acetone, and the reaction similarlycarried out. The product obtained is identified as one having thestructure written hereinabove.

EXAMPLE 2 A. Preparation of 3,3,5,5-tetramethyl-2-morpholone having thestructure ##STR10##

The crude 4M-HEAA obtained in example 1A hereinabove was refluxed withconcentrated HCl (500 ml) for 15 hr and then the HCl is removed in arotary evaporator, to yield a solid 2-morpholone-hydrochloride. Sincethe 2-morpholone-hydrochloride still contains small amounts of water,toluene (600 ml) is added and the mixture was refluxed with a Dean-Starktrap to remove all the water. Thereafter, triethylamine (0.9 mole) wasadded and the mixture refluxed under argon for 10 hr to remove the HClattached to the 2-morpholone so as to form the compound having theabove-identified structure which compound is recovered in better than75% yield as a colorless oil. From the results set forth in Table Ihereinbefore it is evident that the oil has excellent u-v lightstabilization characteristics.

B. Preparation of 3-ethyl-3,5,5-trimethyl-2-morpholone

In a manner analogous to that described in example 2A hereinabove, thesodium 2-[2-methyl-1-hydroxy-2-propylamino]-2-methylbutanoate preparedin example 1B is converted with about 75% yield to a pale oily liquidwhich, upon analysis, is confirmed as having the structure writtenimmediately hereinabove.

C. Preparation of 3,3-pentamethylene-5,5-dimethyl-2-morpholone havingthe structure ##STR11##

In a manner analogous to that described in example 2A hereinabove, thesodium 2-[2-methyl-1-hydroxy-2-propylamino]-2-cyclohexyl carboxylateprepared in example 1C is converted with about 75% yield to awater-white oily liquid which upon analysis, is found to have thestructure written immediately hereinabove.

EXAMPLE 3 A. Preparation of di-(1-hydroxy-2-methyl-2-propyl)amine havingthe structure ##STR12##

0.2 mole of tetramethyl-2-morpholone prepared as described in example 2Ahereinabove, and 200 ml tetrahydrofuran (THF) were placed in athree-necked flask under argon. Lithium aluminum hydride (0.2 mole) wasadded in small portions during a half hour period, after which thereaction mixture was refluxed for 5 hr, then cooled down. 8 ml of 10%NaOH followed by 23 ml distilled water are added with stirring, and themixture was filtered. The solid obtained was rinsed thoroughy with THFand the filtrate concentrated. The essentially pure aminodiol isobtained upon recrystallization or distillation, which has a 90% yield,and it has a mp of 73°-75° C. Upon analysis it is confirmed that it hasthe structure written hereinabove.

As is evident from Table I hereinbefore, the aminodiol has excellent u-vlight stabilization properties.

B. Preparation of(1-hydroxy-2-methyl-2-propyl)(1-hydroxy-2-methyl-2-butyl)amine

In a manner analogous to that described in example 3A hereinabove,3-methyl,3-ethyl-5,5-dimethyl-2-morpholone is reduced with LiAlH₄ toprovide a better than 80% yield of(1-hydroxy-2-methyl-2-propyl)(1-hydroxy-2-methyl-2-butyl)amine which hasa bp of 136°-7° C./4 mm Hg.

C. Preparation of(1-hydroxy-2-methyl-2-propyl)(1-hydroxymethyl-1-cyclohexyl)amine

In a manner analogous to that described in example 3A hereinabove,3,3-pentamethylene-5,5-dimethyl-2-morpholone is reduced with LiAlH₄ toprovide a better than 75% yield of(1-hydroxy-2-methyl-2-propyl)(1-hydroxymethyl-1-cyclohexyl)amine.

EXAMPLE 4 A. Preparation of tetramethyl-monoaza-15-crown-5

A small amount of metallic sodium is added to 0.033 mole ofdi-(1-hydroxy-2-methyl-2-propyl)amine dissolved in t-butanol (250 ml)and triethylene glycol ditosylate (0.033 mole) in p-dioxane (150 ml) wasadded in drops during a 3 hr period at a temperature of 60° C. After theaddition, the reaction mixture was filtered and the solvent wasevaporated. Water was added to the residue and the solution wasextracted with several aliquots of methylene chloride. The mixture wasthen dried and concentrated. Upon distillation puretetramethyl-monoaza-15-crown-5 is obtained (n=3 ethylene oxide units) inbetter than 50% yield and has a bp of 97°-9° C./0.15 mm Hg.

B. Preparation of trimethyl-ethyl-monoaza-15-crown-5

In a manner analogous to that described in example 6A hereinabove,(1-hydroxy-2-methyl-2-propyl)(1-hydroxy-2-methyl-2-butyl)amine isreacted with triethylene glycol ditosylate, and the reaction mixtureworked up to yield about a 50% yield of a colorless oil having a bp of122°-4° C./0.08 mm. The structure of the oil is confirmed by the usualanalysis (n=3 ethylene oxide groups).

C. Preparation of dimethyl-pentamethylene-monoaza-15-crown-5

In a manner analogous to that described in example 6A hereinabove,(1-hydroxy-2-methyl-2-propyl)(1-hydroxymethyl-1-cyclohexyl)amine isreacted with triethylene glycol ditosylate and the reaction mixtureworked up to give about a 50% yield of a colorless oil having a bp of143°-6° C./0.1 mm. The structure of the compound is confirmed byanalysis (n=3 ethylene oxide units).

D. Preparation of tetramethyl-18-crown-6

In manner analogous to that described in example 6A hereinabove, a smallamount of potassium metal was used instead of sodium;di-(1-hydroxy-2-methyl-2-propyl)amine was reacted with tetraethyleneglycol ditosylate, the reaction mixture worked up as before, and acolorless oil was obtained in about 40% yield which oil had a bp of120°-3° C./0.1 mm. Upon analysis the oil is found to betetramethyl-18-crown-6 (n=4 ethyleneoxide units).

E. Preparation of tetramethyl-12-crown-4

In a manner analogous to that described in example 6A hereinabove, asmall amount of lithium metal is used instead of sodium, anddi-(1-hydroxy-2-methyl-2-propyl)amine is reacted with diethylene glycolditosylate. The reaction mixture is worked up as before to give about a15% yield of tetramethyl-12-crown-4 (n=2 ethylene oxide units) which oilhas a bp of 68°-9° C./0.2 mm.

All the crown ethers prepared hereinabove are found to have excellentu-v stabilization properties.

EXAMPLE 5 A. Preparation of 3,3,5,5-tetramethyl-morpholine ##STR13##

3.0 g of di-(1-hydroxy-2-methyl-2-propyl)amine and 25 ml ofmethanesulfonic acid are placed in a round-bottomed flask and heated to130° C. for more than 10 hr after which the reaction mixture is cooleddown and added slowly to a 10% NaOH solution. The mixture is thenextracted with 50 ml aliquots of methylene chloride several times, driedand concentrated. Upon distillation, a colorless oil is obtained inabout 50% yield which boils at 63°-4° C./19 mm. It is found to be anexcellent u-v stabilizer, as is evident from the data in Table I.Analysis by proton nuclear magnetic resonance (nmr) and field desorption(FD) mass spectroscopy confirms the structure of the oil as being3,3,5,5-tetramethyl-morpholine.

B. Preparation of 3,5,5-trimethyl-3-ethyl-morpholine

In a manner analogous to that described in example 5A hereinabove,starting with(1-hydroxy-2-methyl-2-propyl)(1-hydroxy-2-methyl-2-butyl)amine andreacting with methanesulfonic acid, then working up the reactionmixture, a colorless oil having a bp 71°-3° C./20 mm, is obtained inabout 50% yield. Less than 5% by weight of the oil is found to provideexcellent u-v light stability in polypropylene.

C. Preparation of 3,3-dimethyl-5,5-pentamethylene-morpholine

In a manner analogous to that described in example 5A hereinabove,(1-hydroxy-2-methyl-2-propyl)(1-hydroxymethyl-1-cyclohexyl)amine isreacted with methanesulfonic acid and worked up to obtain about a 50%yield of a colorless oil having a bp 86°-9° C./3 mm. Its structure isconfirmed by GC, IR and proton nmr analysis. About 0.5-1.0% by weight inpolypropylene is found to provide excellent u-v stability.

EXAMPLE 6 A. Preparation of N,N'-bis-(1-methoxy-2-methyl-2-propyl)-aminehaving the structure ##STR14##

Sodium hydride (0.24 mole) is washed once with dry toluene, thensuspended in 100 ml toluene. Di-(1-hydroxy-2-methyl-2-propyl)amine (0.1mole) is added and the mixture is slowly warmed to reflux under argon.After about 1 hr the mixture is cooled down to room temperature and analkylating agent such as methyl iodide or dimethyl sulfate (0.22 mole)in 20 ml of toluene is added dropwise over a period of about 1 hr. Thereaction is stirred at ambient temperature overnight, and worked up byadding water, extracting the aqueous solution with toluene, drying thecombined toluene solutions with sodium sulfate, and concentrating. Thedesired N,N'-bis-(1-methoxy-2-methyl-2-propyl)-amine is obtained in pureform by simple distillation, with about a 90% yield. It has a bp of80°-2° C./10 mm Hg.

In a manner analogous to that described in example 6A hereinabove, thefollowing aminodiethers are prepared by reacting the appropriateaminodiol and alkylating agent, respectively, and working up asdescribed to obtain about 80% or better yields of the aminodiethers:

N-(1-methoxy-2-methyl-2-propyl)-N'-(1-methoxy-2-methyl-2-butyl)amine hasa bp of 91°-4° C./10 mm., and,

N-(1-methoxy-2-methyl-2-propyl)-N'-[2-(methoxymethyl)cyclohexyl]aminehas a bp of 111°-4° C./2 mm.

Corresponding nitroxyl compounds of the foregoing compounds may beprepared by conventional procedures such as the one described inSynthetic Communications, 5, 409 (1975). The nitroxyl is generally aorange-red colored oil showing a typical 3-line structure inelctron-spin resonance (esr) spectroscopy.

EXAMPLE 7 Process for preparation of polysubstituted 2-morpholones,whether prior art or novel compounds, and particularly tetra-substituted2-morpholones

The first step in the process of this invention is to prepare a 4M-HEAAhaving the desired substituents. It will be appreciated that thesesubstituents are most conveniently provided by reacting a2,2'-substituted-2-aminoethanol and a monoketone with appropriatesubstituents on either side of the carbonyl C, or benzaldehyde which mayhave ring substituents. As described in Example 1 hereinbefore, the4M-HEAA is formed by reacting the aforesaid appropriately substitutedreactants in the presence of chloroform and, preferably, in the presenceof a phase transfer catalyst. In general, the 4M-HEAA is formed with nosubstituent on the N atom. The 4M-HEAA is then cyclized in the presenceof a concentrated mineral acid as described in Example 2 hereinbefore toform a polysubstituted 2-morpholone having the general structure:##STR15## wherein, R¹, R², R³ and R⁴ are independently selected from thegroup consisting of aryl, alkyl having from 1 to about 24 carbon atoms,cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbonatoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkylhaving from 1 to about 18 carbon atoms; and,

R¹ and R² together, or R³ and R⁴ together, or each pair, may be cyclizedforming a ring having from about 5 to about 8 carbon atoms;

except that not more than one of R¹, R², R³ or R⁴ maybe hydrogen; and nomore than three of R¹, R², R³ and R⁴ may be cyclic.

The N atom may be substituted, if desired, with a substituent R⁵selected from the group consisting of O, lower alkyl having from 1 toabout 6 carbon atoms, and hydroxyalkyl having from 1 to about 6 carbonatoms. Such substitution is preferably effected soon after formation ofthe 4M-HEAA, before it is cyclized, since in most instances, making thesubstitution after the 2-morpholone is formed, is more difficult becauseof the hindrance of the substituents on the N-adjacent C atoms. As willbe evident upon consideration of the problem posed by the highlyhindered nature of the N atom, particularly if it is tetra-substitutedrather than only tri-substituted, it is surprising that cyclization ofthe 4M-HEAA is effected at all by the mineral acid.

A. Preparation of 5,5-dimethyl-3-phenyl-2-morpholone

In a manner analogous to that described in Example 1A hereinbefore,2-amino-2-methyl-1-propanol, benzaldehyde and chloroform are reacted atice bath temperature in the presence of a phase transfer catalyst andaqueous NaOH is added dropwise into the reaction vessel while thecontents are being stirred. The sodium salt of the compound is recoveredwith an analogous workup, and warmed with a mineral acid to yield acompound which is a hydrochloride. When the hydrochloride is reactedwith triethanolamine, the compound recovered is identified as being5,5-dimethyl-3-phenyl-2-morpholone.

B. Preparation of [2'-(2'-cyanopropyl)]-3,5,5-trimethylmorpholin-2-one

In a manner analogous to that described in Example 1A hereinbefore,2-amino-1-propanol, chloroform and 4-cyano-4-methyl-2-butanone arereacted in the presence of a phase transfer catalyst with the additionof aqueous NaOH (50% solution) to form a sodium salt which is recoveredand warmed with conc HCl to form the morpholone hydrochloride to whichtriethanolamine is added so as to yield a compound which is identifiedas being [2'-(2'-cyanopropyl)]-3,5,5-trimethylmorpholin-2-one.

C. Preparation of 5-methyl-3-phenyl-3-ethyl-2-morpholone

In a manner analogous to that described in Example 1A hereinabove,2-amino-1-propanol, chloroform and phenylethylketone are reacted toyield a sodium salt which is recovered and cyclized with conc HCl toyield a morpholone hydrochloride which upon reaction withtriethanolamine yields a compound identified as being5-methyl-3-phenyl-3-ethyl-2-morpholone.

D. Preparation of3-[2-(2'-cyanopropyl)]-3,5-dimethyl-hydroxyethyl-morpholin-2-one

In a manner analogous to that described in Example 1A hereinbefore,2-amino-2-methyl-1,3-propanediol is reacted with4-cyano-4-methyl-2-butanone and chloroform, optionally in the presenceof a phase transfer catalyst, with the addition of aqueous NaOHsolution, to yield a sodium salt. The salt is cyclized upon warming withconc HCl to yield a polysubstituted morpholone hydrochloride which uponreaction with triethanolamine yields a compound identified as being3-'2-(2'-cyanopropyl)1-3,5-dimethyl-hydroxyethyl-morpholin-2-one.

E. Preparation of 5-hydroxymethyl-3,5,5-trimethyl-2-morpholonerepresented by the structure ##STR16##

In a manner analogous to that described in Example 1A hereinbefore,2-amino-2-methyl-1,3-propanediol is reacted with chloroform in excess,and acetone in large excess, optionally in the presence of a phasetransfer catalyst, with the addition of aqueous NaOH solution, to yielda sodium salt. The salt is cyclized upon warming with conc HCl to yielda polysubstituted morpholone hydrochloride which upon reaction withtriethanolamine yields a compound identified as having the structuregiven immediately hereinabove.

F. Preparation of 5-hydroxymethyl-5-ethyl-3,3-dimethyl-2-morpholone

In a manner analogous to that described in Example 1A hereinbefore, thereaction of 2-amino-2-ethyl-1,3-propanediol with chloroform in excess,and with acetone in large excess, with the addition of aqueous NaOHsolution, yields a sodium salt which is cyclized with conc HCl to yieldthe compound identified as having the structure given immediatelyhereinabove.

I claim:
 1. A polysubstituted morpholine having the structure: ##STR17##wherein, R¹, R², R³ and R⁴ are independently selected from the groupconsisting of aryl, alkyl each having from 1 to 24 carbon atoms,cycloalkyl having from 5 to 7 carbon atoms, aralkyl having from 7 to 20carbon atoms, cyanoalkyl having from 2 to 12 carbon atoms, ether havingfrom 4 to 18 carbon atoms, and hydroxyalkyl having from 1 to 18 carbonatoms, so that each C atom on either side of the N atom isdisubstituted;R¹ and R² together, or R³ and R⁴ together, or each pair,may be cyclized forming a ring having from 5 to 8 carbon atoms; R⁵ isselected from hydrogen, oxygen, and alkyl having from 1 to 24 carbonatoms, and hydroxyl; except that not more than three of R¹, R², R³ or R⁴may be cyclic.
 2. The compound of claim 1 wherein one of R¹ and R² is Hand the other and R³ and R⁴ are each lower alkyl having from 1 to 6carbon atoms.
 3. The compound of claim 1 wherein R¹ and R² are eachlower alkyl having from 1 to about 6 carbon atoms, one of R³ and R⁴ isH, and the other is phenyl or cyanoalkyl having from 2 to 12 carbonatoms.
 4. The compound of claim 1 wherein R¹, R², R³ and R⁴ are eachlower alkyl having from 1 to 6 carbon atoms.
 5. The compound of claim 1wherein R³ and R⁴ are together cyclized to form substituted orunsubstituted phenyl or cycloalkyl.
 6. The polysubstituted morpholine ofclaim 1 selected from the group consistingof:3,3,5,5-tetramethyl-morpholine; 3,5,5-trimethyl-3-ethyl-morpholine;and, 3,3-dimethyl-5,5-pentamethylene-morpholine.